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Catalytic advances enable methane conversion without coking

By Scott Jenkins |

The large supply of unconventional natural gas from shale deposits in the U.S. has increased attention on utilizing small alkanes to synthesize higher-value chemicals and fuels, while avoiding thermal steam-cracking, which is energy-intensive. Attempts to catalytically convert methane, ethane and propane to industrially relevant chemicals, such as methanol, ethylene, propylene and others, require activation of the relatively inert carbon-hydrogen bond in alkanes. A team of researchers from Tufts University (Medford, Mass.; www.tufts.edu) has advanced the effort toward catalyst-aided reaction of small alkanes in a series of recent papers.

In one study, published in Nature Chemistry, the team investigated a methane conversion catalyst system designed to avoid the problem of deactivation by coke buildup, which has plagued many platinum- and nickel-based catalyst systems in this area. Both can activate C–H bonds, but tend to dehydrogenate alkanes completely, leading to coking. The Tufts researchers investigated a single-atom alloy (SAA) composed of 1% individual, isolated platinum atoms in a copper surface. Copper is resistant to coking, but does not have the ability to activate C–H bond breakage. So the introduction of dispersed, individual atoms of platinum in the copper matrix facilitates catalytic activity without the coke formation.

The development of SAA catalysts was enabled by scanning tunneling microscopy imaging of Charlie Sykes, a Tufts chemistry professor who led the study. “Using this surface-imaging technique, we could visualize model surfaces with single-atom resolution and relate these structures to the chemistry that we observed,” Sykes remarks.

“By distributing Pt atoms in a copper surface, we lose some activity, but we gain significantly in our ability to use Pt in the only form that can give us the dehydrogenation products we want at low temperatures and without deactivation,” says Maria Flytzani-Stephanopoulos, a Tufts professor of chemical engineering who co-led the research. The experimental work at Tufts was aided by Michail Stamatakis at University College London, who performed quantum calculations.

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